| Title: |
Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights |
| Authors: |
Logallo, Alessandra; Maddock, Lewis C. H.; Mu, Manting; Gravogl, Lisa; Jin, Na; Peñas de Frutos, Marconi Nicolás; Karsten, Meyer; García Melchor, Max; Hevia, Eva |
| Publisher Information: |
Wiley-VCH GmbH |
| Publication Year: |
2024 |
| Collection: |
UVaDOC - Repositorio Documental de la Universidad de Valladolid |
| Subject Terms: |
Amide; Cobalt; Fluoroarenes; Iron; Metalation; 2303 Química Inorgánica |
| Description: |
Producción Científica ; Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6-tetramethylpiperidide), s-block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth-abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M−H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C-H metalation occurs leaving C−F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions. ; Swiss National Science Foundation (SNF) (projects numbers 206021_ 177033 and 188573), the University of Bern, the Irish Research Council (GOIPG/2021/88, M.M.), and the University of Valladolid (CONVREC-2021-221, M.N.P.-D.) |
| Document Type: |
article in journal/newspaper |
| File Description: |
application/pdf |
| Language: |
English |
| Relation: |
https://doi.org/10.1002/anie.202402907; Angewandte Chemie International Edition, april 2024, e202402907; https://uvadoc.uva.es/handle/10324/67702; Angewandte Chemie International Edition |
| DOI: |
10.1002/anie.202402907 |
| Availability: |
https://uvadoc.uva.es/handle/10324/67702; https://doi.org/10.1002/anie.202402907 |
| Rights: |
Attribution-NonCommercial-NoDerivatives 4.0 Internacional ; info:eu-repo/semantics/openAccess ; http://creativecommons.org/licenses/by-nc-nd/4.0/ ; © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH |
| Accession Number: |
edsbas.776534FE |
| Database: |
BASE |